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Measurement of polyacrylamide polymers in water and wastewater using an

in-line UV–vis spectrophotometer

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DOI: 10.1016/j.jece.2014.02.015

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 Journal of Environmental Chemical Engineering 2 (2014) 765–772

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Measurement of polyacrylamide polymers in water and wastewater using an in-line

UV–vis spectrophotometer
Fares A. Al Momani, Banu Örmeci*
Department of Civil and Environmental Engineering, Carleton University, 1125 Colonel By Drive, Ottawa, ON K1S 5B6, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Measurement of polymers in water and wastewater is a major challenge, and there is currently no quick
Received 21 November 2013 and simple method that can achieve this. This study presents a method for quantification of polyacrylamide
Accepted 24 February 2014 concentration using an in-line UV–vis spectrophotometer that can generate real-time data. Absorbance
spectra of seven polymers were established in the wavelength range of 191.5–750 nm and the highest
Keywords:
absorbance was recorded at 191.5 nm for all polymers. UV absorbance of the polymers gradually decreased
Measurement
Polymer between 191.5–240 nm and a strong linear relationship (R2 > 0.97) between concentration and absorbance
Acrylamide held at 191.5, 200 and 210 nm. Detection limits were established in distilled water and in four other samples
Wastewater collected from water and wastewater treatment plants. Polymer chemistry and presence of organic and
Water inorganic impurities impacted the detection limits. In distilled water samples, the lowest detection limit
measured was 0.05 mg/L. In samples collected from water and wastewater treatment plants, detection
limits varied between 0.07 and 1.35 mg/L depending on the polymer type and water quality. Polymers are
known to be toxic to aquatic ecosystems and they are suspected carcinogens, and the presented method
could be useful in monitoring the polymer concentrations and minimizing its excessive use.
c 2014 Elsevier Ltd. All rights reserved.

Introduction of these methods. In addition, starch-triiodide method, viscosity,

Large quantities of water-soluble polymers are used for water and
wastewater treatment in treatment plants around the world [1]. Poly-
mers are required in wastewater treatment to improve the efficiency
of sludge thickening and dewatering, and in drinking water treatment
as flocculants to remove suspended solids [2–5]. Synthetic polymers
can increase the size and strength of flocs formed by alum or iron-
based coagulants [6]. Moreover, they can replace inorganic coagu-
lants with significant improvement on filter run times and sludge
quantities. Synthetic polymers also substantially reduce the volume
of solids generated and result in important savings in sludge han-
dling and disposal costs [7,8]. Using too little or too much polymer
negatively impacts the treatment efficiency; therefore, it is important
to use polymers at their optimum dose [9]. This ideally requires the
ability to measure and adjust the polymer dose in-line and real-time.
Polymers are also known to be toxic to aquatic ecosystems and they
are suspected carcinogens; therefore preventing their excessive use
is important.
Analytical and chemical methods that are currently available for
measuring polymer concentrations can neither achieve in-line nor
real-time measurements. Commonly used methods for polymer de-
tection include gas chromatography (GC), high-performance liquid
chromatography (HPLC), mass spectrometry (MS) and combination
* Corresponding author.
E-mail address: banu ormeci@carleton.ca (B. Örmeci).
calorimetry, turbidimetry, fluorescence spectrometry, colloid titra-
tion, radioactive labeling, flow injection analysis, size exclusion chro-
matography (SEC), nuclear magnetic resonance (NMR) spectroscopy,
fluorescence tagging, and spectrophotometric determination using
cationic dyes were also used [1,6,10–19]. Difficulties in reproducing
measurements in complex environmental samples were reported by
Dentel et al. [20].
Previous studies reported various laboratory techniques to mea-
sure polymer concentration in water and wastewater samples.
Keenan et al. [21] used SEC and reported a detection limit of 20 μ g/L
in nanopure water and 66 μ g/L in alum sludge supernatant. Becker
et al. [6] employed fluorescence tagging and reported a detection
limit of 10 μ g/L in purified water and 100 μ g/L in water samples
collected from a drinking water reservoir. Gehr and Kalluri [13] used
colloid titration and test suspension methods to measure residual
polymer concentration in sludge filtrate and reported 0.6 mg/L for
colloid titration and 0.1 mg/L for test suspension methods for the
same sample. Chang et al. [1] measured the residual polymer con-
centration in filtrate from a belt press filter using NMR and reported
that the residual polymer concentration was approximately 8 mg/L.
They also reported that the polymer measurements done using charge
titration, viscosimetry and NMR analyses for the same sample showed
little agreement, and higher recoveries were obtained with the NMR
method.

2213-3437/$ - see front matter  c 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2014.02.015
766 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772
Recently, Gibbons and Örmeci [22] developed a spectrophotomet-
ric method to measure polymer concentration in water using a bench-
top UV–vis spectrophotometer. UV–vis measurements are quick, sim-
ple, and accurate, and can find successful applications in research and
industry. It was shown that a strong linear relationship existed be-
tween polymer concentration and sample absorbance in pure water,
and polymer concentration could be determined using a calibration
curve. The tested polymers strongly absorbed light in the wavelength
range of 200–220 nm and the detection limits were reported to be
around 0.5 mg/L at 200 nm. The researchers also noted that the detec-
tion limits may vary with different polymers, and using the specific
absorbance maxima for each polymer would increase the sensitivity
of the method and enhance the detection limit.
The objectives of this study were given as follows: (1) to test the
performance and sensitivity of the spectrophotometric method us-
ing an in-line UV–vis spectrophotometer that is developed for water
quality monitoring at water and wastewater treatment plants, (2) to
determine statistically established detection limits for a range of poly-
mers in distilled water as well as in samples collected from water and
wastewater treatment plants, (3) to evaluate the effect of water qual-
ity on detection limits, and (4) to investigate the effect of dilution on
detection limits. New generation of in-line spectrophotometers pro-
vide accurate measurements in real-time, and a successful method for
in-line and real-time measurements of polymer concentration could
find possible applications in research as well as in water and wastew-
ater treatment.
Materials and methods
Polymers
In the first phase of experiments, seven polyacrylamide poly-
mers (Hydrex 3591, 3593, 3596, 3661, 3572, MagnaFloc LT 27AG
and FloPolymer CB 4350) were tested with distilled water to estab-
lish their detection limits and characteristics of their UV absorbance
spectra. In the second phase, three polymers (Hydrex 3572, FloPoly-
mer CB 4350, and MagnaFloc LT 27AG) were tested in water samples
collected from water and wastewater treatment plants. Hydrex is
manufactured by Veolia Inc., MagnaFloc LT 27AG by BASF Inc. and
FloPolymer CB 4350 is manufactured by SNF Inc. Hydrex 3572 and
MagnaFloc LT 27AG are polymers that are used for water treatment,
and FloPolymer CB 4350 is used for sludge dewatering. The character-
istics, product use, appearance and density of the polymers are listed
in Table 1.
Preparation of stock polymer solution
Stock polymer solutions were prepared at a concentration of 0.01%
for spiking in the samples. The polymers were prepared using a jar
test apparatus (Phipps and Bird, USA) by mixing 0.1 g polymer in
1000 mL of deionized water at a speed of 220 rpm for 5 min, followed
by mixing at a speed of 125 rpm for 55 min. After the initial 1-h of
mixing, the solution was mixed with a hand-held blender for 10 s,
and left to sit for 1 h before use in the experiments. This procedure
produced a well-dissolved polymer solution for all polymers. Polymer
stock solutions were prepared daily.
Water samples
Polymers are widely used for sludge dewatering in wastewater
treatment and for coagulation and flocculation of particles in wa-
ter treatment. Therefore, water matrices used in the experiments in-
cluded (1) distilled water (control); (2) sludge centrate collected from
a wastewater treatment plant (Treatment Plant A); (3) sludge centrate
obtained by centrifuging anaerobically digested Treatment Plant A
sludge in the laboratory for 15 min at a speed of 14,000 rpm; (4) raw
water (before any treatment) collected from a water treatment plant
(Treatment Plant B); (5) clarified water after flocculation and set-
tling from Treatment Plant B. Treatment Plant A is located in Quebec
(Canada) and Treatment Plant B is located in Ontario (Canada). The
names of the treatment plants are withheld based on their request.
Dilution of samples
The water and wastewater samples were diluted after polymer ad-
dition and before absorbance measurements. The following dilution
procedure was used. First, the sample was spiked with polymer to
give the desired polymer concentration. Then, the sample and poly-
mer mixture were mixed for 2 min at 90 rpm and its absorbance
spectrum was measured. Afterwards, the sample was diluted with
distilled water at a ratio of 1:30 or 1:50, and its absorbance spectrum
was measured again.
Absorbance measurements
The in-line UV–vis spectrophotometer (Real Spectrum Platinum
Series) used is manufactured by Real Tech Inc. (Ontario, Canada) and
provides real-time analysis across the entire spectrum of UV and/or
visible light (Fig. 1). The instrument combines high wavelength reso-
lution with the power of a deuterium light source as used in high-end
lab spectrophotometers, and provides accurate and sensitive spec-
trum analysis. The spectral range is extended into the visible region
with the addition of a tungsten light source. The instrument is used at
water and wastewater treatment plants for real-time and in-line mea-
surement of total organic carbon, disinfection by-product precursors,
nitrate, and UV transmittance for UV disinfection. The instrument has
a sampling frequency of 1 min and has a wavelength resolution of
1 nm. The recommended working range is between 0 and 1 A.U.
In this study, the absorbance values were measured between
191.5–750 nm and no significant absorbance was detected from poly-
mer samples above 260 nm. Therefore, the results are presented in
the wavelength range of 191.5–300 nm.
Statistical analysis
All experiment sets were repeated at a minimum of three times.
For each replicate, a newly prepared polymer stock solution was used
and a minimum of seven data points were recorded at each poly-
mer concentration. Regression lines for the calibration curves were
established using 95% confidence intervals (C.I.)
The US EPA (US Environmental Protection Agency) approved
method detection limit (MDL) was used to determine the statistically
established detection limits as explained in Berthouex and Brown
[23]. MDL is the minimum concentration of a substance that can be
measured with 99% confidence that it is greater than zero. The method
controls against false positives due to noise and utilizes at least seven
replicates at low concentrations. In this study, seven replicates were
used for each concentration.
Results and discussion
The experiments were carried out in two phases. In Phase 1, dis-
tilled water was used to establish the minimum detection limits and
observe the differences in the absorbance spectra of seven polymers.
In Phase 2, a range of water and wastewater samples were used to
establish the minimum detection limits for three polymers in differ-
ent water matrices. During the testing, polymer concentrations were
varied between 0.05 mg/L and 20 mg/L, and detection limits were
established at 191.5, 200 and 210 nm.
 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772 767

Table 1
Characteristics of polymers.

Polymer Type Charge Product use Appearance Density (kg/m3 )

Hydrex 3591 Polyacrylamide Anionic Potable water treatment Crystalline powder 750
Hydrex 3593 Polyacrylamide Anionic Potable water treatment Crystalline powder 750
Hydrex 3596 Polyacrylamide Anionic Potable water treatment Crystalline powder 600–900
Hydrex 3661 Polyacrylamide Cationic Potable water treatment Crystalline powder 600–900
Hydrex 3572 Polyacrylamide Anionic Potable water treatment Crystalline powder 750
MagnaFloc Polyacrylamide Anionic Potable water treatment Granular powder 750
LT 27AG
FloPolymer Polyacrylamide Cationic Sludge dewatering Crystalline powder NA
CB 4350

3661 polymers, respectively. Similar absorbance spectra were also ob-

Fig. 1. The experimental set-up includes the in-line UV–vis spectrophotometer (Real-
Tech Inc.) that is mounted on the wall, a pump and a magnetic stirrer.
tained from polymers Hydrex 3591, 3593, 3596, MagnaFloc LT 27AG
and FloPolymer CB 4350 (data not shown). The absorbance measure-
ments were performed in the wavelength range of 191.5–750 nm and
the highest absorbance values were recorded at 191.5 nm for all poly-
mers. UV absorbance of the polymers gradually decreased between
191.5 and 240 nm and there was no significant absorbance beyond
240 nm. Incremental increases in polymer concentrations resulted in
incremental increases in absorbance values indicating a linear rela-
tionship between polymer concentration and UV absorbance of the
samples. The absorbance values measured ranged from 0.005 to 1.27
(A.U.) for the concentration range of 0.05–20 mg/L. Although the ab-
sorbance measurements for very low (<0.2 mg/L) polymer concen-
trations showed some noise, the UV–vis spectrophotometer was still
able to detect very small (0.1 mg/L) increments of polymer increases
(Figs. 2a and 3a).
The linear relationship between the polymer concentration and
sample absorbance allows the construction of a calibration curve to
determine the unknown polymer concentrations in water. When the
absorbance of water samples at 191.5 nm was plotted against the
polymer concentration, a strong linear relationship based on a 95%
C.I. was found (insets of Figs. 2 and 3). Linear relationship between
concentration and absorbance also held at 200 and 210 nm, but the
slopes of the regression lines were lower indicating that the method
would be less sensitive at these wavelengths. For example, the slopes
of regression lines at wavelengths 191.5, 200 and 210 nm for con-
centration range of 0.05–1 mg/L were 0.047, 0.0192 and 0.0056 for
Hydrex 3572 and 0.038, 0.0147 and 0.0045 for Hydrex 3661, respec-
tively.
Detection limits for seven polymers were established in distilled
water using the EPA approved MDL method (Table 2). No dilution was
needed since distilled water did not contain any organic or inorganic
contaminants that absorb light. Detection limits were established at
191.5, 200 and 210 nm, and the lowest detection limits were obtained
at 191.5 nm where the method is most sensitive. Detection limits for
all polymers were lower than 0.1 mg/L at 191.5 nm. The method was
able to detect as low as 0.05 mg/L for Hydrex 3572, 3661, and 3596
polymers, which confirms the very high sensitivity of the absorbance
measurements at 191.5 nm. The detection limits were slightly higher
for Hydrex 3593 (0.09 mg/L), Hydrex 3591 (0.1 mg/L), MagnaFloc LT
27AG (0.06 mg/L) and FloPolymer CB 4350 (0.08 mg/L) at the same
wavelength.

Phase 1: establishing detection limit in distilled water Phase 2: establishing detection limits in different water matrices

Absorbance spectra of seven polymers (Hydrex 3591, 3593, 3596,
3661, 3572, MagnaFloc LT 27AG and FloPolymer CB 4350) were deter-
mined in distilled water in three concentration ranges: 0.05–1 mg/L,
1–10 mg/L, and 10–20 mg/L. The selected concentration ranges al-
low the determination of minimum detection limits for each polymer
and also show the performance and sensitivity of the method at low,
medium and high polymer concentrations. Figs. 2 and 3 show the ab-
sorbance spectra from samples containing Hydrex 3572 and Hydrex
Table 2 provides the detection limits measured at 191.5, 200, and
210 nm in different water matrices and with different polymers. The
descriptions of the water and wastewater samples are provided in the
Materials and Methods section.
Detection limits in centrate collected from a wastewater treatment plant
Known concentrations of polymers Hydrex 3572 and FloPolymer
CB 4350 were spiked in centrate collected from Treatment Plant A
768 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772

Table 2
Detection limits measured at 191.5, 200, and 210 nm in different water matrices and with different polymers.

Sample Dilution Polymer Detection limit (mg/L)

191.5 nm 200 nm 210 nm

Distilled water
Distilled water No dilution Hydrex 3572 0.05 0.06 0.07

Distilled water No dilution Hydrex 3591 0.10 0.11 0.12

Distilled water No dilution Hydrex 3593 0.09 0.09 0.13

Distilled water No dilution Hydrex 3661 0.05 0.06 0.07

Distilled water No dilution Hydrex 3596 0.05 0.06 0.07

Distilled water No dilution FloPolymer CB 4350 0.08 0.10 0.15

Distilled water No dilution MagnaFloc LT 27AG 0.06 0.09 0.13

Centrate (full-scale)
Centrate 1:30 Hydrex 3572 1.20 1.90 2.10

Centrate 1:50 Hydrex 3572 0.25 0.89 1.3

Centrate 1:30 FloPolymer CB 4350 − − −

Centrate 1:50 FloPolymer CB 4350 0.35 0.78 1.10

Centrate (lab-scale)
Centrate 1:30 Hydrex 3572 − − −

Centrate 1:50 Hydrex 3572 0.85 1.13 1.65

Centrate 1:50 FloPolymer CB 4350 1.35 2.10 2.05

Clarified water
Clarified water 1:30 Hydrex 3572 0.73 1.23 1.45

Clarified water 1:30 MagnaFloc LT 27AG 0.09 0.15 0.17

Raw water
Raw water 1:30 Hydrex 3572 0.63 0.99 1.30

Raw water 1:30 MagnaFloc LT 27AG 0.07 0.09 0.15

(referred to as full-scale centrate in Table 2), and absorbance spectra
of the samples were measured. Centrate was used as it is without any
pretreatment. FloPolymer CB 4350 is the polymer that is currently
used at Treatment Plant A. Preliminary testing indicated that dilution
was needed due to the high absorbance of the centrate, and samples
were diluted with distilled water at a ratio of 1:30 or 1:50. It should be
noted that the centrate had a strong yellowish color likely caused by
the ferric products used during treatment. The polymer concentration
was varied from 0.1 to 10 mg/L.
Fig. 4a and b shows the centrate absorbance at different Hydrex
3572 concentrations using 1:30 and 1:50 dilution ratios between 200
and 300 nm. Maximum absorbance values were again obtained at
191.5 nm. The inset figures focus on the wavelength range between
191.5 and 220 nm where significant absorbance from polymer was
observed. It can be seen that polymer concentrations as low as 0.2 mg/
L could be detected, but no significant difference was observed below
0.2 mg/L, which was later confirmed by the method detection limits
established in centrate (Table 2).
The linear relationship between the centrate absorbance and
polymer concentration was observed at three selected wavelengths
(191.5 nm, 200 nm and 210 nm) and at both dilution ratios (1:30
and 1:50) (Fig. 5a and b). The dotted lines show the 95% C.I. for the
regression lines. Since the absorbance of the samples were highest
at 191.5 nm, the slopes of the regression lines were also highest
at 191.5 nm, suggesting that this would be the wavelength that is
most sensitive to changes in the polymer concentration. In addition
to Hydrex 3572, FloPolymer CB 4350, was also tested under the same
conditions, and similar results were obtained (data not shown).
These results point to the importance of dilution factor and the de-
pendence of MDL on the dilution factor. For example, a dilution factor
of 1:30 resulted in an MDL value of 1.2 mg/L for Hydrex 3572. In con-
trast, increasing the dilution ratio to 1:50 resulted in an MDL value of
0.25 mg/L for the same polymer. These results indicate that by opti-
mizing the dilution factor, the detection limits can be improved even
further. Dilution should aim to bring down the sample absorbance
to the working range of the instrument. At a dilution rate of 1:30,
 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772
Fig. 2. Absorbance spectra of the Hydrex 3572 polymer in distilled water. (a) Concen-
tration from 0.05 to 1 mg/L, (b) concentration from 1 to 10 mg/L and (c) concentration
from 10 to 20 mg/L. Insets: linear regression (95% C.I.) of the sample absorbance and
polymer concentration at 191.5 nm.
the working range of the instrument (0–1 A.U.) was substantially
exceeded which resulted in lower sensitivity and higher detection
limits.
Calculations carried out with FloPolymer CB 4350 resulted in an
MDL value of 0.35 mg/L for a dilution ratio of 1:50. When the dilution
ratio was lowered to 1:30, the absorbance of the sample exceeded
1.5 A.U. and no significant difference could be observed among low
polymer concentrations due to the loss in sensitivity. Consequently,
MDL could not be established for FloPolymer CB 4350 at a dilution
ratio of 1:30 (Table 2).
Detection limits in centrate obtained by centrifuging sludge in the labo-
ratory
Centrate collected from the treatment plant and used in the previ-
ous experiments naturally included some residual polymer that was
added during sludge dewatering. In order to obtain centrate samples
769
Fig. 3. Absorbance spectra of the Hydrex 3661 polymer in distilled water. (a) Concen-
tration from 0.05 to 1 mg/L, (b) concentration from 1 to 10 mg/L and (c) concentration
from 10 to 20 mg/L. Insets: linear regression (95% C.I.) of the sample absorbance and
polymer concentration at 191.5 nm.
that did not contain any residual polymer, anaerobically digested
sludge collected from Treatment Plant A was centrifuged in the labo-
ratory (referred to as lab-scale centrate in Table 2). Centrifuged cen-
trate was spiked with two polymers (Hydrex 3572 and FloPolymer
CB 4350) as indicated in Table 2. The same dilution ratios (1:30 or
1:50) were again used with this centrate. A dilution ratio of 1:30
brought the absorbance values down to 1.5 at 191.5 nm, which were
still above the ideal working range (0–1 A.U.) of the instrument and
resulted in saturated absorbance and a flat line (Fig. 6a). Due to this
reason, significant differences in absorbance values between the in-
cremental increases of polymer could not be observed (Fig. 6a) and
a method detection limit could not be established (Table 2). Linear
regression analysis at 95% confidence interval at wavelengths 191.5,
200 and 210 nm produced flat lines with R2 values 0.47, 0.97, and
0.59, respectively.
Increasing the dilution ratio to 1:50 resulted in incremental in-
creases in absorbance values with incremental increases in polymer
770 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772

Fig. 4. Absorbance spectra of the Hydrex 3572 polymer in centrate collected from a
wastewater treatment plant. (a) Dilution 1:30, and (b) dilution 1:50. Insets show the Fig. 6. Absorbance spectra of polymers in centrate obtained by centrifuging sludge in
absorbance spectra in the wavelength range of 191.5–220 nm. the laboratory. (a) Hydrex 3572 with dilution ratio of 1:30 and (b) FloPolymer CB 4350
with dilution ratio of 1:50.

concentrations (Fig. 6b). The sensitivity of the spectrophotometric

measurements was much improved and increments of 0.1 mg/L poly-
mer could be detected. Linear regression of the absorbance and con-
centration data resulted in a well-defined linear relationships with
R2 values greater than 0.97 at 191.5, 200 and 210 nm. The linear re-
gression at 191.5 nm had the highest slope and indicated that lowest
detection limits could be obtained at this wavelength. The MDL values
for Hydrex 3572 and FloPolymer CB 4350 were calculated as 0.85 and
1.35 mg/L, respectively (Table 2).

Detection limits in raw and clarified water

Raw (untreated) and clarified (after settling) water samples were
collected from a drinking water treatment plant (Treatment Plant B),
and tested with Hydrex 3572 and MagnaFloc LT 27AG polymers in
the concentration range of 0.1–10 mg/L. MagnaFloc LT 27AG was the
polymer that was used at the treatment plant. Fig. 7a and b shows
the absorbance spectra of clarified and raw water samples at a di-
lution rate of 1:30. The inset figures confirm the linear relationship
between absorbance values and polymer concentrations at 191.5, 200
and 210 nm with R2 values greater than 0.97. As expected, the highest
absorbance values were measured at 191.5 nm and there was no sig-
nificant absorbance beyond 240 nm. For clarified water, MDL values
were determined as 0.73 mg/L and 0.09 mg/L for Hydrex 3572 and
MagnaFloc LT27 AG polymers, respectively (Table 2). For raw water,
the MDL values were 0.63 and 0.07 for the same polymers (Table 2).
Results in Table 2 illustrate that the sensitivity of the polymer mea-
surements is affected by the water quality and presence of organic and
inorganic matter. Hydrex 3572 was tested in different water matri-
ces and the calculated MDL value ranged from 0.05 to 1.2 mg/L. At a
dilution ratio of 1:30, Hydrex 3572 had an MDL value of 1.2, 0.73 and

Fig. 5. Linear regression (95% C.I.) of the sample absorbance and Hydrex 3572 concen-
tration at 191.5, 200, and 210 nm. (a) Dilution 1:30, and (b) dilution 1:50.
 F.A. Al Momani, B. Örmeci / Journal of Environmental Chemical Engineering 2 (2014) 765–772
Fig. 7. Absorbance spectra of Hydrex 3572 and MagnaFloc LT 27AG polymers in raw
and clarified water at dilution ratio of 1:30. (a) Clarified water and Hydrex 3572, and
(b) MagnaFloc LT 27AG and raw water.
0.63 mg/L in centrate (full-scale), clarified water and raw water and
no MDL value could be established for the lab-scale centrate since the
sample absorbance exceeded the working range of the spectropho-
tometer. The full-scale centrate had a COD (chemical oxygen demand)
of 761 mg/L and a turbidity of 195 NTU. The lab-scale centrate, on
the other hand, had a COD of 895 mg/L and a turbidity of 285 NTU,
which explains the observed difference between the detection limits
in these two water matrices.
Water quality measurements in the raw and clarified water sam-
ples collected from Treatment Plant B showed that the raw water
had a higher turbidity (5.98 NTU) compared to the clarified water
(0.5 NTU). However, the MDL of the clarified water (0.73 mg/L) was
higher than the MDL of the raw water (0.63 mg/L). This was likely
caused by the residual polymer in the clarified water that remained
from the coagulation and flocculation process.
There is very little information available on the residual poly-
mer concentrations in samples collected from water and wastewater
treatment plants after a process that involves polymer addition (e.g.,
coagulation and flocculation, sludge conditioning and dewatering).
Gehr and Kalluri [13] measured 0.6 mg/L and 0.1 mg/L in sludge fil-
trate using colloid titration and test suspension methods respectively.
Chang et al. [1] compared the performance of the NMR, viscosity mea-
surement, and colloid titration methods for the same sludge filtrate
and reported 8 mg/L, 1.18 mg/L and 0.11 mg/L respectively as the
measured values. The results indicated that the NMR method was
more sensitive compared to the other two methods which likely un-
derestimated the actual polymer concentrations in previous studies.
However, the NMR method required significant preparation time for
analysis and the results were difficult to reproduce particularly in
complex water matrices [1].
771
The spectrophotometry based method presented herein is quick
and simple and it is useful for research and product testing. The de-
tection limits illustrated in centrate indicate that the method has the
sensitivity to determine the residual polymer concentrations dur-
ing sludge conditioning and dewatering, and it may be used as an
optimization tool after establishing typical baseline readings and ab-
sorbance variations for each treatment plant. The method may also
find applications in monitoring coagulation and flocculation pro-
cesses at water treatment plants; however, its sensitivity is close
to the limit of 1 mg/L which is the maximum polymer dose that can
be added to raw water set by the Phase II of the Safe Drinking Wa-
ter Act (1992) in the US, and therefore further improvements to the
method may be needed. Future research should be geared towards
testing and validating the method at full-scale treatment plants and
determining whether it has promise for full-scale applications. Future
research is also recommended to test the performance of the method
for industrial applications including petroleum and mining industries
where large quantities of polymers are used and residual oil and other
constituents in wastewater can interfere with the method.
Conclusions
The results from this study indicate that polyacrylamide polymers
used for water and wastewater treatment strongly absorb light in the
191.5–230 nm wavelength range, and the peak absorbance was mea-
sured at 191.5 nm for all of the seven polymers tested in this study.
The detection limits in distilled water were different for different
polymers and depended on polymer type and chemistry. In addition,
presence of organic and inorganic impurities in water samples im-
pacted the detection limits. In distilled water samples, the detection
limits were below 0.1 mg/L for all polymers at 191.5 nm. The lowest
detection limit measured was 0.05 mg/L. For raw and clarified water
and centrate samples collected from treatment plants, the detection
limits varied between 0.07 and 1.35 mg/L depending on the poly-
mer type and impurities in the sample. Choosing the right dilution
range also improved the sensitivity of the method and lowered the
detection limits. The in-line UV–vis spectrophotometer used in this
study provided a powerful tool for accurate and sensitive measure-
ment of polymer concentration. The method has strong potential for
research and industrial applications where the process flow charac-
teristics do not change significantly. For water and wastewater treat-
ment applications, it needs to be tested at full-scale treatment plants
to determine whether it can successfully be used to measure and ad-
just the polymer dose under varying water quality parameters and
operational conditions.
Conflicts of interest
None declared.
Acknowledgments
This study was funded by the Natural Sciences and Engineering Re-
search Council of Canada (NSERC) under the Engage program (Project
number: EGP 434904-12) in collaboration with the Pathogen Detec-
tion Systems Inc. (Ontario, Canada). The authors would like to thank
RealTech Inc. (Ontario, Canada) for loaning the in-line UV–vis spec-
trophotometer during the duration of the study.
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